Azo dyestuffs



Patented Feb. 16, 1937 2,070,997 I I u AZOKDYESTUFFS Emil Eduard Misslin, Basel, and Rudolf von Capeller, Riehen, Switzerland, assignors to the firm of Society of Chemical Industry in Basle,

Basel, Switzerland V "KLNO; Drawing; Application September 25, 1935, Ser ial,1*Io.--42,144. In Switzerland September It has been found that new and valuable azodyestuffs are obtained by uniting with diazocompounds the new hydroxy-naphthalene-sulfonic acids themselves obtainable by acylating the two amino-groups of the heteronuclear 1,3-

diamino-hydroxynaphtha1ene-sulfonic acids (cf. German Patent No. 92,239). According to the nature of the acylating agents, the heteronuclear 1,3-diamino-hydroxynaphthalene-sulfonic acid,

and the diazo-compound used there are obtained acid wool dyestuffs, dyestuffs for lacquers, or also direct dyeing dyestuffs. By the expression heteronuclear 1,3-diamino-hydroxynaphthailene-sutfonic acids there are understood such compounds which contain OH and SO3H groups in that six membered ring of the naphthalene nucleus which does not contain the two NHz-groups.

Valuable dyestuffs are particularly obtained from the 1,3-diamino-8-hydroxynaphthalene-6- sulfonic acid and the 1,3-diamino-5-hydroxynaphthalene-S-sulfonic acid. These dyestuffs are obtained by uniting diazo-compounds of the general formula (R meaning any desired radical .of the benzene or naphthalene series) with the hydroxynaphthalene-sulfonic acids of the general formula l 1 N-acyl z N-acyl 40 wherein one 1 stands for an OH-group and the other 11 for a hydrogen atom, one :1: stands for a SO3H-group and the other :0 for a hydrogen atom, and wherein further a hydrogen atom lies between the Oil-group and the SO3I-I-group,

45 whereby there are obtained dyestuffs of the general formula a Y a 10 claims. (01.26042) a;

in whichrone ystandsfor anOH group-and' the. other y for a hydrogen atom,;-0.ne jzr stands for-a SOsH-group,,and the other an; for a N -I, T-R- group wherein R means. any desired aromatic radical of the benzene or naphthalene series and, 5

thalene-sulfonic acids of the above cited general l5 formula, wherein acyl'stands for radicals of aliphatic carboxylic acids (such as formyl, acetyl, chloracetyl or propionyl radicals), and. combining the'same with ortho-hydroxylated or-ortho carboxylated diam-compounds, there are pro duced dyestuffs which can be converted into metalliferous dyestuffspwhich may be used'for' dyeing wool byfurther treatment in substance or on the fiberwith agents yielding metal.- Par-" ticularly valuable dyestuffs-are obtained when using the new intermediate product's themselves obtainable by aroylating 1,3-diamino-8-hydroxynaphthalene-fi-sulfonic'- acid, *for example, with benzoyl chloride, metaor para-nitrobenzoyl chloride, uor ,B-naphthoyl chloride, those dyestuffs being of special value which are produced with aroylating agents containing nitro-groups, and by reducing the condensation products thus obtained and containing the nitro-groups. These products are particularly valuable bothas coupling components for theflmanufacture of dyestuffs capable of being diazotized onthe fiber, and as diazotizingcomponents? It must be noted that the dyestuffs of this invention are also obtainable by combining the 40" non-acylated heteronuclear 1,3 diamino hydroxy-naphtha1ene-su1fonic acids first with a dia-zo-compound under such conditions that the OH-group only isof importance for the formation of theazo-dyestuff, and then treating the dyestufi thus obtained with a suitable acylating agent and, if desired, subjecting this product to a cautious saponification or reduction.

The following examples illustrate the invention, the parts being by weight:---

Example 1 In the present specifica- 10 ess.

there is obtained an azo-dyestuff oi the formula OH IIIHCOCH:

SOINB NHCOCH;

which dyes wool bright red. A cotton dyestuff is obtained with dehydrothiotoluidine. V

- In like manner 1,3-diamino- 5-hydroxy-naphthalene-7-sulfonic acid may be used in theproc- Products of like properties are produced by treating 1,3-diamino-8-hydroxynaphthalene-6- sulfonic acid with benzoyl chloride. Thus the azodyestufi of the formula SOsNB made from 1,3-dibenzoyl-diamino-8-hydroxynaphthaleneJLsulfonic acid and diazo-benzene dyes wool in an acid bath pure bluish-red. When substituting the para-toluenesulfochloride for the benzoyl chloride there is also obtained an intermediate product which also leads to wool dyestuifs with simple diazo compounds, such as diazobenzene-sulfonic acid, diazo-toluene-sulfonic acid ordiazo-naphthalene-sulifonic acid.

Example 2 parts of 1,3-diamino-8-hydroxy-naphthalene-G-sulfonic acid are suspended in 1000 parts of water heated to 50-60 C. and are cautiously neutralized with anhydrous sodium carbonate. There are then added 50-parts of calcium carbonate and 94 parts of meta-nitrobenzoylchloride,

introduced in small portions.- The calcium salt droxynaphthalene-G-sulfonic acid separates and,

SOzNa when cool, is filtered. This calcium salt is stirred into 2000 parts of hot, waterand converted, by m ans of anhydrous. sodium carbonate. into the soluble sodium salt of the same acid. The whole is filtered hot, allowed to cool and from it the sodium salt of the 3,3"-dinitro-dibenzoyl-1,3-diamino-8-hydroxynaphthalene-fi-sulfonic acid is salted out by addition of sodium chloride.

For the reduction parts of this sodium salt are dissolved in about 2000 parts of hot water. The solutionis allowed to run gradually into a reducing mixture, boiling under reflux and well stirred, of 1000 parts of water, 300 parts of iron turnings and 30 parts of acetic acid. When the whole has been run in, the mixture is boiled for another half-an-hour under reflux, anhydrous sodium carbonate is added until all the iron has.

been'precipitated and the whole is filtered hot from ferruginous mud. The filtrate is acidified with acetic acid and the 3',3"-diamino-dibenzoyl- 1,3-diamino 8 hydroxy naphthalene-6 -sulfonic acid is salted out.

The procedure is similar when para-nitro-benzoyl-chloride is used instead of meta-nitrobenzoylchloride. These new intermediate products, when coupled with diazo-compounds, yield dyestuffs which are characterized by high afiinity to cellulose or regenerated cellulose. Thus the aniline or ortho-toluidine-dyestufis dye cotton bluered tints which can be diazotized on the fibre and further developed. With beta-naphthol extraordinarily strong yellowish-red dyeings are obtained.

If the amino-aroylated compounds are acylated there are obtained products which already have substantive character. They can, therefore, be converted into dyestuffs on the fibre. The dyestuif from ortho-diazotoluene and meta,meta"- diacetyl-amino-dibenzoyl 1,3 diamino 8 hydroxy-naphthalenee6-sulfonic acid of the formula ITIHCOCHa CH3 0 H NHC o-O soma- -NHC 0-C NHOOOH: dyes cotton bright bluish-red tints.

Dyestuffs can also be made by tetrazotizing the new coupling components and coupling with suitable diazo-compounds. For example, the reduced condensation product from 1 mol. 1,3-diamino-8- hydroxynaphthalene-6-sulfonic acid and 2 mols nitrotoluic acid chloride (CH3ZNO2:COC1=1:2:4) and meta-toluylene-diamine yields a. dyestuff dyeing cotton yellow which by further development on the fibre with diazotized para-.nitraniline yields an intense brown. The dyestuff corresponds very probably with the formula I NH,

no NEG o-goirgg rhlwgrwl on. NH, 1 that? 4N1];

Example 3 23.7 parts of the para-toluenesulfonic acid ester of 1 amino 8-hydroxynaphthalene-3,6-disulfonic acidv of the formula om-Osm-w NH:

HOlS S OaH 0H NHdO-QNH:

corn

are dissolved in 600 parts of water and the'solution is cooled to 0 C. There are then added 12 parts of hydrochloric acid of 30 per cent. strength, and while well stirring 17.5 parts of a sodium nitrite solution of 20 per cent. strength is causedto fiow into the liquid beneath its surface. When diazotization is complete 7.2 parts of (if-naphthylamine, dissolved in the form of hydrochloride are added. The coupling proceeds very well without further addition and stirring is continued overnight. After addition of 8 parts of anhydrous sodium carbonate and 40 parts of a sodium hydroxide solution of 40 per cent. strength the monoazo-dyestufi produced is dissolved, 17.5 parts of a sodium nitrite solution of 20 per cent. strength are added at 0-5 C. and indirect diazoi tizing'is produced by adding in a single dose, While stirring well; 30 parts of hydrochloric acid of 30 per cent. strength. Stirring is continued for 2 hours at -15 C. The separated diazo-compound is filtered and suspended in 1000 parts of ice-water. This diazo-compound of the monoazodyestuff is run into a cold solution of 24.6 parts of SOxNB.

4 ,4 -diamino-dibenzoyl- 1,3-diamino-8-hydroxynaphthalene-G-sulfonic acid and parts of anhydrous sodium carbonate in 500 parts of water and the whole is stirred for some hours. When coupling is complete the disazo-dyestufi is salted out, filtered and stirred into 500 parts of sodium S O|Na S oiNa dissolves in ,water to'a blue solution and dyes cotton blue tints which when diaZotiZedandcOu-J.

v qrn, some NHC o-ONH,

Also instead of 4*,4"-diamino-dibenzoyl-1,3-diamino-8-hydroxy naphthalene 6 sulfonic acid the reduced condensation product from 1,3-diamino 8 hydroxynaphthalene-6-sulfonic acid and meta-nitro-benzoylchloride or the nitrotoluic acid chloride named in the foregoing example may beused.

' iems 4 l 30.3 parts 0f B-naphtl iylamine4l,8-disulfonic' acid are diazo-tized in the usual mariner coupled with amaphthylamine, further diazotizedand the diazo-compound of this monoazo-dyestuff, if necessary, salted out and isolated by filtration. It is suspended in about 400 parts of water and the suspension is run into a cold solution of 50 parts of dissolves in water to a blue solution and dyes cotton blue tints which by diazotization and coupling with phenylmethyl pyrazolone become green and fast to washing.

In this case also 'inst ead of the middle component named, other middle components may be used, for instance cresidine or para-xylidine or even 1-amino-2-methoxynaphthalene; as the initial component various aromatic sulfonic acids of the benzene or naphthalene series can be used. Thus, forexampleythe dyestuff from l-amino- 2.5 dichlorobenzene-4esulfonic acid as initial component and 1eammo-2-met 0 yI1 ph h ene- 1 fi-sulfonic acid as middle component corresponds to the formula Also here there are obtained quite similar dyestufis when using the 4,4'-diaminobenzoyl-1,3- diamino 8-hydroxynaphthalene-S-sulfonic acid as final component.

The dyestuffs obtained in analogous manner from the 4,4-diaminobenzoylor 3,3'-diamino benzoy1-1,3-diami'no hydroxynaphthalene-7- sulfonic acid have very similar properties.

Thus the dyestufi of the formula so H- 0011. a

SOJH

represents a dark powder which dissolves in water to blue solutions, dyes cotton similar tints, and,

when diazotized on the fiber and developed with 1-p-henyl-3-methy1-5-pyrazolone, dyes the same fast green tints. l.

Example 5 23.7 parts of para-toluenesulfonic'acid ester of l-amino 8 hydroxynaphthalene-3,6-disulfonic acid of the formula SOZH are dissolved in 600 parts of water and the solution is cooled to 0 C. There are then added 12 parts of hydrochloric acid of 30 per cent. strength and, while stirring well, 17.5 parts of a solution of 20 per cent. strength of sodiumnitrite introduced beneath the surface of the liquid. When diazotization is complete there are added 7.2 parts 30 per cent. strength, while stirring well. After a further 2 hours stirring at -15 C. the precipitated diazo-compound is filtered and suspended in 1000 parts of ice-water. Into this suspension is run a solution of 11.2 parts of a mixture of 1-naphthylamine6sulfonic acid and l-naphthylamine-7-sulf0nic acid, dissolved in 200 parts of water in the form of sodium salts; buffering with sodium acetate and. stirring overnight fol-,- low. The disazo-dyestufi thus formed is salted out,- is filtered and suspended in ice-water. To

.NHC o-O-NH.

the suspensionis added sufficient sodium hydroxide solution to dissolvethe disazo-dyestufl and the whole is diazotized indirectly with the calculated quantity of sodium nitrite and hydrochloric acid. After about 2 hours, the diazotization being at an end, the -diazo-compound is salted out, filtered and well suspended in ice-water. The suspension is run into a cold solution of 24.6 parts of 3',3"- or 4',4"diamino-dibenzoyl-l,3 diamino-8-hydroxynaphthalene fi-sulfonic acid and parts of anhydrous sodium carbonate in 500 parts of water and the mixture is stirred for some hours. When coupling is complete the trisazo-dyestuff is salted out, filtered and stirred into 500 parts of sodium hydroxide solution of 2 per cent. strength; for saponification of the toluene-sulfoester the mixture is warmed for about hour at Gil-70 C.; neutralized with acetic acid and filtered to'separate the saponifiedtrisazodyestuff of the general formula in which one y stands for a sOsH-group and the other 11 for a hydrogen atom, and in which in each of the benzene nuclei one at stands for an aminogroup and the other a for a hydrogen atom. It forms a dark powder which dissolves in water to a blue solution and dyes cotton blue tints which, when diazotized and developed with phenylmethylpyrazolone, become green and fast.

Dyestuffs of similar dyeing properties are obtained when one of the initial components named in .Example 4 is; substituted for the 1,8-a-minonaphthol derivative used in this example and when other middle components are used. Thus,

S OINB N- N' N=N N= N som mm mm:

SOIN'8 GIN! OaN! OgNQ SOaNa O;Na SOzNl! dye cotton bluetints which, when diazotized on the fiber and developed with 1-pheny1-3-methyl- 5-pyrazolone, become green and fast.

What we claim is:

1. The dyestuffs of the general formula a: N-acyl l N-acyl in which one 3/ stands for an OI-I-group and the other 1! for a hydrogen atom, one 2: stands fora SOaH-group and the other a: for a -N=NR- group wherein R means the radical oi an aminono NacoQ-nn,

NBC o-O-Nm azo-dyestuff and in which the N=N-R-group stands in o-position to the OH-group, which products are more or less dark powders, dissolving in water to violet, to blue and blue-green solutions, and dyeing the fiber similar tints.

3. The dyestuffs of the general formula in' which one y stands iEor'an ol I group and the othery 'for a hydrogen atom,'one ic 'sta-nds for a sOsH-group and the other, :c for a N=NR- group wherein R means the radicahofan aminoazo-dyestuif and in which the -N=NR-, group stands in o-position to the OH-group, and in which in each of the benzene nuclei one :1: stands for an amino-group and the other'a: for a hydrogen atom, which products are more or less dark powders, dissolving in water to red, to violet, to blue and green solutions, andi'dyeing the cotton fiber similar tints, which, when .diazotized on the fiber and developed with 1-phenyl-3-methyl-5-- pyrazolone, dye the same intensively green tints of good fastness, particularly to washing. 5. The dyestuffs of the general formula wherein in each of the benzene nuclei one :1: stands for an amino-group and the other :r for a hydrogen atom, and R stands for the radical of an azodyestufi containing at lea'stbne naphthalene nucleus," which produt'sare moreor less dark powders dissolving in water to blue to green solutions and dyeingthevegetable fiber similar tints which, when diazotized \on the fiber and developed with 1-phenyl 3-methyl-5-pyrazolone, dye the same intensively green tints of good fastness, particularlyto washing.

61 1119 dyestuffs or the gene al formula Y I wherein in each of the benzene nuclei one at stands for an amino-group and the other :1: for a hydrogen atom, and R stands for the radical of a mono- -'intensively:-green tints of good :larly to'washing; A

azo-dyestufi' containing at least-one naphthalene nucleus, which products are-more or less dark powders dissolving in water to blue to green solutions and dyeing the vegetable fiber similar tints which, when diazotized on the fiber and developed with 1-phenyl 3-methyl-5-pyrazolone, dyethe sameintensively green tints of good fastness, particularly to washing.

7. The'dyestufis of the general formula OH HFQI WQ" H o HOaS wherein in each of the benzenenuclei onex'stands for an amino-group and the other at for a hydrogen atom, and R stands for the radical of a disazodyestufi containing at least one naphthalene nucleus; which products are more or less dark powders dissolving in water to blue to green solu- I tions and dyeing the vegetable fiber similar tints which, when diazotized on'the fiber and developed same intensively green tints of ticularly to washing.

8. The dyestufis of the general formula good fastness, parwherein in each of the benzene nuclei one a: stands for an amino-group and the other a: for a hydrogen atom, which products are more or less dark powders dissolving in water to blue solutions and dyeing the vegetable fiber similar tints which, when diazotized on the fiber-and developed with 1-phenyl-3-methyl-5-pyrazolone, dye the same fastness, particu- 2,070,997 '7 10. The dyestuffs of the general formula when diazotized on the fiber and developed with SOIH wherein in each of the benzene nuclei one a: 1-pheny1-3-methy1-5-pyrazo1one, dye the same stands for an amino-group and the other a: for intensively green tints of good fastness, particu- 15 a. hydrogen atom, which products are more or less larly to washing. 15

dark powders dissolving in water to blue solutions EMIL EDUARD MISSLIN. and dyeing the vegetable fiber similar tints which, RUDOLF VON CAPELLER. 

